US5201961A - Photovoltaic device containing organic material layers and having high conversion efficiency - Google Patents
Photovoltaic device containing organic material layers and having high conversion efficiency Download PDFInfo
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Definitions
- the present invention relates to a photovoltaic device comprising three organic layers disposed between two electrodes, of which at least one of said electrodes is light transmittable, wherein the three organic layers consist of and are arranged either as a layer of organic electron acceptor (hereinafter referred to as "OEA") material (a), a layer of organic electron donor (hereinafter referred to as "OED") material (b) and a layer of OED material(c) different from OED material(b); or as a layer of OED material(d), a layer of OEA material (e), and a layer of OEA material(f) different from OEA material (e); arranged in this order from the light-incident side.
- OED organic electron acceptor
- a photovoltaic device Since the purpose of a photovoltaic device is to convert light energy into electric energy (voltage ⁇ current), a primary measure of the device is its conversion efficiency.
- organic semiconductors with a high conversion efficiency used in devices of this type are limited to p-type materials. Accordingly, materials of low work function such as Al, In and Mg must be used for the electrode, but, unfortunately, such materials are readily oxidized.
- An internal electric field generated upon bonding an n-type inorganic semiconductor and a p-type organic semiconductor is utilized in this junction.
- CdS, ZnO or the like are used as the n-type material and merocyanine dyes, phthalocyanine dyes, etc. as the p-type organic semiconductor material.
- An internal electric field generated upon the bonding of an OEA material and an OED material is utilized in this device.
- OEA material dyes such as malachite green, methyl violet and pyrylium, and condensed polycyclic aromatic compounds, such as, flavanthrone and perylene pigment are used and as examples of the OED material, phthalocyanine pigments, merocyanine dyes, etc. are used.
- the conversion efficiency of a photovoltaic device using an organic material is lower than that using an inorganic semiconductor.
- One of the most important reasons for this phenomenon is that the short circuit-photocurrent (herein referred to as "Jsc") is low.
- Jsc the short circuit-photocurrent
- the Jsc value of the device described above is much lower than this. This is ascribed to a low quantum efficiency and a narrow photosensitive wavelength region.
- the photosensitive wavelength region should preferably extend from 400 nm to longer wavelengths to provide a region as wide as possible; however, photosensitive wavelength regions of commercial devices are often at shorter wavelengths and narrower regions than the desired values.
- the fill factor (herein referred to as "ff") is frequently low.
- Low ff can be attributed to a decrease in the quantum efficiencies exhibited by an organic semiconductor at low electric field. Therefore, to improve the ff value, it is preferable to develop a device consisting of a structure which can form an intense internal electric field and does not suffer a decrease in efficiency.
- ff will be increased if a device structure is constructed in which formed carriers can easily reach an electrode without an energy barrier. That will lead to an improvement in the open circuit voltage (herein referred to as "Voc”), but so far these factors have not been sufficiently considered.
- photocarriers are mainly formed in an organic material layer, such a junction cannot avoid a limitation due to its photosensitivity.
- This limitation results because an organic material layer is usually formed with a single material and because an organic semiconductor having an intense absorption, from 400 to, for instance, 800 nm wavelength does not exist at present. Accordingly, although the device of this structure can overcome the problems of light transmittance of an electrode on a light-incident side and the stability of the electrode, high conversion efficiency cannot be achieved because of its narrow photosensitive wavelength region.
- This junction is the most desirable one at present relative to the two other structures described above.
- Light can be irradiated through a transparent electrode and, as photocarriers can be formed in an interfacial region existing in the two different layers, the photosensitivity region can also be widened.
- carriers are formed by the perylene pigments at 450-550 nm wavelength and by copper phthalocyanine at 550-700 nm wavelength.
- the ff is greater than with other device structures, one can assume that a high internal electric field is formed.
- Tang's device does have some disadvantages.
- a second disadvantage concerns the electrode material.
- the electrode In Tang's invention, the electrode must be in ohmic contact with each of the organic layers. Also in his report, it is described that the Voc is reduced in a device structure, in which the sequence order of organic layers is reversed. This is estimated to be attributable to a deterioration of the ohmic contact described in his invention.
- the ohmic contact is sufficient, there is another problem with the stability of the metal material of the electrode, because a metal having an ohmic contact with an OEA material will necessarily have a low work function.
- Ag, Sn and Al are exemplified in the patent literature, all of which are readily oxidized.
- a photovoltaic device containing a portion comprising three organic layers disposed between two electrodes, of which at least one of said electrodes is light transmittable, wherein the three layers consist of and are arranged as a layer of OEA material (a), a layer of OED material (b) and a layer of OED material (c) different from OED material (b); or as the same three layers except that an OEA material is to be read as an OED material and an OED material as an OEA material, respectively; arranged in this order from the light-incident side.
- FIGS. 1 to 4 are, respectively, schematic views illustrating specific examples of the device structure according to the present invention.
- One object of the present invention is to provide a photovoltaic device containing a portion comprising three organic layers disposed between two electrodes, of which at least one of said electrodes is light transmittable; wherein the three layers consist of and are arranged either as a layer of OEA material(a), a layer of OED material (b) and a layer of OED material (c) different from OED material (b); or as three layers (d), (e) and (f), except that an OEA material is to be read as an OED material and an OED material as an OEA material respectively; arranged in this order from the light-incident side.
- Another object of the present invention is to provide a photovoltaic device, wherein an n-type inorganic semiconductor layer is placed between a light transmittable electrode and an organic layer or between a back side electrode and an organic layer in addition to the component comprising the three organic layers described above.
- a further object of the present invention is to provide an organic material photovoltaic device having high values of Voc, Jsc and ff and possessing superior photoelectronic conversion efficiency as a result of the device structure.
- FIG. 1 One embodiment of the photovoltaic device of the present invention is shown in FIG. 1.
- a support can also be placed on a side of a back side electrode.
- FIG. 2 shows another and more preferable device structure of the present invention. The difference between FIGS. 1 and 2 is that a light transmittable n-type inorganic semiconductor layer is interposed in FIG. 2.
- FIG. 3 shows still another embodiment of the photovoltaic device according to the present invention.
- FIG. 4 shows still another embodiment of the present invention.
- FIGS. 3 and 4 The difference between FIGS. 3 and 4 is that an n-type inorganic semiconductor layer is interposed in FIG. 4.
- FIG. 2 is representative of the device according to the present invention.
- One feature of the device structure of the present invention resides in that a layer of OEA material (a) (hereinafter referred to as “layer a”), a layer of OED material (b) (hereinafter referred to as “layer b”), and a layer of OED material (c) (hereinafter referred to as “layer c”) are all laminated. It has been found that the Jsc is particularly improved with this structure than with a structure in which only layer a and layer b are laminated.
- the photocarrier forming site is present at the interface between layer a and layer b, with no particular difference from the structure without layer c, and that the Jsc is increased because of a remarkable increase in the photocurrent formed in layer b.
- the thickness of layer b should be within a certain range, for, if the thickness is too large, then the Jsc is lowered. In view of the above, the following reasons are assumed for the increase of Jsc.
- photo active site The portion of layer b in which photocarriers are formed (hereinafter referred to as "photo active site”) is at the interface in contact with layer a. If its thickness is within an appropriate range for increasing the Jsc and is, for example, from 100 to 200 ⁇ , then an electric short-circuit is caused in a device structure without layer c. If the thickness of layer b is increased to avoid the short-circuit, then the portion not contributing to the formation of the photocarriers (hereinafter referred to as "photo inactive site”) increases.
- the thickness of the photo active site is thin as described above, light absorption in this region is incomplete and a considerable portion of the light reaches the photo inactive site and is wastefully absorbed in this region.
- layer c made of a material different from (b)
- electric short-circuiting can be prevented.
- the incident light at a wavelength which is absorbed in the photoactive site of layer b to form photocarriers is not absorbed in layer c as in layer b, it is reflected at the back side electrode and not suffering significant decay, then contributes again to a formation of photocarriers in the photo active site. As a result, in the structure having layer c, the amount of light absorbed in the light active site in layer b is increased.
- layer c made of a material different from that of layer b means that the absorption wavelength region of layer b does not completely overlap with that of layer c.
- the difference between the wavelengths of the absorption peaks for layer b and for layer c is not less than 20 nm.
- n-type inorganic semiconductor layer results in an improvement of the conversion efficiency and reduction of short-circuiting is achieved as a result of the improvement of Voc, Jsc and ff.
- a transparent electrode As a transparent electrode, a material with a low Fermi level, such as ITO is conventionally used. Therefore, if the n-type inorganic semiconductor layer is not present, a Schottky junction is formed between layer a and the transparent electrode. This junction works as an energy barrier when electrons move from layer a to the transparent electrode. If the n-type inorganic semiconductor layer is present, the contact between each of transparent electrode/n-type inorganic semiconductor layer and n-type inorganic semiconductor layer/layer a can be an ohmic contact. In this case, different from the case in which the electrode and the organic layer are in direct ohmic contact, electrons can move smoothly due to the presence of the n-type inorganic semiconductor layer therebetween.
- Electrons are supplied in the dark from the n-type inorganic semiconductor layer to layer a and the internal electric field formed at the interface between layers a and b is strengthened.
- a difference of levels at the edge portion of the transparent electrode (usually greater than about 1000 ⁇ in the case of using ITO) is moderated due to the presence of the n-type inorganic semiconductor layer, and the occurrence of short-circuits between both electrodes is reduced in this portion.
- layer b adjacent thereto forms a pn junction with the n-type inorganic semiconductor layer, and eliminates the effect of the pinholes in layer a. Also when pinholes are present in layer b, a similar result is obtained between the back side electrode and layer a. Accordingly, short-circuits are scarcely observed.
- glass or plastic films can be used as a transparent insulative support used in the present invention.
- ITO Indium oxide, zinc oxide, and semi-transparent Au and the like can be used.
- the preferred thickness of the materials is 100 to 10,000 ⁇ .
- n-type semiconductor layer in the present invention for example, zinc oxide, zinc oxide doped with a trivalent metal, CdS, titanium oxide, amorphous silicon doped with phosphorus and n-type crystalline silicon can be used.
- zinc oxide, trivalent metal-doped zinc oxide, CdS or titanium oxide is used when a transparent electrode is required.
- the thickness is from 10 to 10,000 ⁇ when light transmission is necessary and it can be thicker when light transmission is not necessary.
- OEA material used in the present invention as layers a, e and f, there can be mentioned, for example, the following:
- Perylene series pigment Pigment Red (hereinafter referred to as "PR") 179; PR 190; PR 149; PR 123; Pigment Brow 265; etc.
- Perynone series pigment Pigment Orange 43; PR 194; etc.
- Anthraquinone series pigment PR 168; PR 177; Vat Yellow 4; etc.
- Dyes such as crystal violet; methyl violet and malachite green; etc. and acceptor compounds such as fluorenone; 2,4,7-trinitro-fluorenone; tetracyanoquinodimethane and tetracyanoethylene.
- vapor deposition is preferable.
- the preferred thickness of the film is 100 to 3,000 ⁇ .
- phthalocyanine series pigments such as Au, Zn, Co, Ni, Pb, Pt, Fe, and Mg
- metal free phthalocyanines such as aluminum chlorophthalocyanine, indium chlorophthalocyanine, and gallium chlorophthalocyanine
- chlorinated copper phthalocyanine chlorinated zinc phthalocyanine
- oxygen-coordinated phthalocyanine such as vanadyl phthalocyanine and titanyl phthalocyanine
- Quinacridone series pigment Pigment Violet 19, Pigment Red 122, etc.
- Dyes such as, merocyanine compounds, cyanine compounds and squalium compounds
- High molecular material having ⁇ -electron conjugation and high molecular material having ⁇ -electron conjugation containing lone pair electrons are shown below as examples:
- Heterocyclic polymers such as polythiophene, poly-(substituted thiophene), polypyrrole, poly(substituted pyrrole), polyfuran, poly-(substituted furan), polyindole and polycarbazole;
- Amine type polymers such as polyaniline, poly(substituted aniline), polydiphenylamine, poly(N,N'-diphenylbenzidine), polydiaminonaphthalene, polytriphenylamine and polyaminopyrene;
- Condensed ring polymers and condensed polycyclic polymers such as poly-p-phenylene and polyazulene.
- conjugated polymers can be synthesized by chemical polymerization or electrochemical polymerization.
- Charge transport agents used in organic electrophotographic light sensitive bodies such as, hydrazone compounds, pyrazoline compounds, triphenylmethane compounds, triphenylamine compounds, styryl compounds, benzodithiol series compounds, oxadiazole compounds, oxazole compounds, and polyvinyl alcohols.
- Electron donative compounds used in electroconductive organic charge transfer complexes such as, tetrathioflavalene and tetraphenyl tetrathioflavalene.
- phthalocyanine is particularly preferable as the material of layer b.
- phthalocyanine can also absorb light at wavelengths longer than 600 nm.
- many OEA materials absorb light only of wavelengths shorter than 600 nm. Accordingly, a photocurrent can be formed over the entire visible light region from short wavelengths to long wavelengths at the organic material pn interface which is a photocurrent-generation site and, as a result, wide photosensitivity can be realized;
- both the crystalline and the amorphous phase of molecular arrangement can exhibit excellent but different functions.
- phase is crystalline or amorphous can be confirmed by observing a film, prepared on a glass substrate, with a polarization microscope under cross Nichol.
- phthalocyanine series pigments, indigo or thioindigo series pigments, and quinacridone series pigments are stable in a crystalline phase and can form a film of a specific crystal form, for example, by vapor deposition.
- merocyanine compounds, cyanine compounds, squalium compounds and charge transfer agents used in electrophotography often form an amorphous molecular arrangement when fabricated into a film by a vapor deposition method.
- phthalocyanine series pigments including metal-free phthalocyanine/quinacridone series pigments; phthalocyanine series pigments/ merocyanine compounds; phthalocyanine series pigments/cyanine compounds; phthalocyanine series pigments/squalium compounds; indigo series pigments/quinacridone pigments; phthalocyanine series pigments/charge transport agents and quinacridone series pigments/charge transport agents can be exemplified.
- a particularly preferable example of the crystalline materials of layer c used in the present invention is quinacridone series pigments. For instance, there can be mentioned:
- hydrazone compounds pyrazoline compounds, triphenylmethane compounds, triphenylamine compounds and styryl compounds, each having an alkylamino group or an arylamino group, can be exemplified.
- These layers can be formed as films, for example, by vapor deposition, spin coating, dipping and electrochemical polymerization. Among them, vapor deposition is most preferable to obtain a thin, uniform film.
- the appropriate film thickness is 30 to 300 ⁇ for layer b. If it becomes too thick, no increase is obtained for Jsc. On the other hand, if it is too thin, the light absorption of the layer itself is lowered and Jsc is reduced.
- An appropriate film thickness for layer c is from 50 to 10,000 ⁇ .
- the back side electrode of the present invention when it is in contact with the OED material layer, metals with high work function such as Au, Pt, Ni, Pd, Cu, Cr, and Ag, and when it is in contact with the OEA material layer, Al, In, Pb, Zn, Mg, and Ag can be used. Further, when the electrode is in contact with the n-type inorganic semiconductor layer, all the metals described above, can be used.
- the thickness of the metal film is preferably 50 to 3,000 ⁇ .
- Zinc oxide was deposited on an ITO glass substrate (30 ⁇ / ⁇ , manufactured by MATSUZAKI SHINKU, Co.), being cleaned well and kept at a temperature of about 250° C., as a thin film of a thickness about 1,500 ⁇ , by an RF magnetron sputtering method using argon as the sputtering gas.
- a film of about 400 ⁇ perylene tetracarboxylic acid bismethylimide (hereinafter referred to as "PLME”), which is an electron acceptor material
- PLME perylene tetracarboxylic acid bismethylimide
- AlClPc chloroaluminumphthalocyanine
- QA quinacridone
- H 2 Pc metal-free phthalocyanine
- a device was fabricated by the procedures of Example 1 except the thickness of the PLME layer was changed to 500 ⁇ and the AlClPc layer was replaced with a titanyl phthalocyanine (hereinafter referred to as TiOPc) layer having a thickness of 120 ⁇ and the conversion efficiency was measured.
- TiOPc titanyl phthalocyanine
- ZnPc zinc phthalocyanine
- a device was fabricated by the procedures of Example 1 except the thickness of the AlClPc layer was changed to 120 ⁇ and the QA layer was replaced with a 2,9-dimethylquinacridone layer.
- a device was fabricated by the procedures of Example 1 except the thickness of the PLME layer was changed to 450 ⁇ and the QA layer was replaced with a layer of pyrazoline compound of the following formula having a thickness of 400 ⁇ .
- a device was fabricated by the procedures of Example 10 except the thickness of the pyrazoline compound layer was changed to 200 ⁇ . Two electrodes of the device were short-circuited and monochromatic light having a wavelength of 740 nm with an intensity of 30 ⁇ A/cm 2 was irradiated from a side of ITO. A photocurrent Jsc of 4.6 ⁇ A/cm 2 was obtained and the quantum yield calculated from the Jsc value was 29%.
- a device was fabricated by the procedures of Example 10 except the layer of pyrazoline compound was replaced with a layer of phenylene diamine compound of the following formula having a thickness of 300 ⁇ .
- Example 17 The pigment 2 in Example 17 was replaced with the following pigment 3 and a layer of zinc oxide was disposed thereover in thickness of 1,500 ⁇ in the same manner as in Example 1. In this case, the substrate was not heated intentionally. Finally, a layer of silver was disposed by vapor deposition as a back side electrode.
- N,N'-diphenylbenzidine (3.5 mmol/l) and tetrabutyl ammonium perchlorate (hereinafter referred to as "TBAP”) (0.1 mmol/l) were dissolved in acetonitrile and electrochemically polymerized on the ITO glass as used in Example 1 at a potential of 1.5 V relative to a saturated calomel electrode (hereinafter referred to as "SCE") for 7 seconds, using a Pt plate as a counter electrode.
- SCE saturated calomel electrode
- the resultant film was electrochemically undoped at 0.5 V relative to the SCE and sufficiently cleaned with methanol.
- a poly(N,N'-diphenylbenzidine) with a film thickness of about 900 ⁇ was obtained.
- Aniline was subjected to chemical oxidative polymerization by using peroxoammonium disulfate as an oxidizer under an acidic condition with sulfuric acid.
- the resultant polyaniline was undoped with an aqueous ammonia and then washed with water sufficiently. It was dissolved into N-methylpyrrolidone to prepare a coating solution.
- a layer of zinc oxide on ITO glass prepared in the same manner as in Example 1 a layer of PLME of about 500 ⁇ thickness and then a layer of H 2 Pc of about 100 ⁇ thickness were disposed by a vacuum vapor deposition and the solution containing polyaniline was coated thereover by spin coating to produce a polyaniline film in about 1,000 ⁇ thickness.
- Gold was vapor deposited under vacuum as a back side electrode and lead wires were attached with silver paste to two electrodes.
- 3-Hexylthiophene (0.1 mol/l) and TBAP (0.1 mol/l) were dissolved in nitrobenzene and polymerized by the constant potential polymerization method using platinum as a working electrode.
- the thus formed poly(3-hexylthiophene) was electrochemically reduced and sufficiently washed with methanol.
- the polymer was dissolved in toluene to prepare a coating solution.
- the solution was coated by spin coating on an ITO glass/PLME (500 ⁇ thickness)/AlClPc (100 ⁇ thickness) prepared in the same manner as in Example 24 to form a poly(3-hexylthiophene) layer of about 600 ⁇ thickness.
- Gold was further vapor deposited as a back side electrode on the layer and the photoelectronic conversion characteristics were measured in the same manner as in Example 1.
- Voc 0.52 V
- Jsc 2.68 mA/cm 2
Abstract
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JP2131319A JPH03263380A (en) | 1989-11-27 | 1990-05-23 | Photovoltaic element |
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Cited By (21)
Publication number | Priority date | Publication date | Assignee | Title |
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DE19854938A1 (en) * | 1998-11-27 | 2000-06-08 | Forschungszentrum Juelich Gmbh | Component used as a solar cell or LED, has layers separated by an interlayer containing one or both layer materials and a different conductivity material colloid |
WO2001039276A1 (en) * | 1999-11-26 | 2001-05-31 | The Trustees Of Princeton University | Organic photosensitive optoelectronic device with an exciton blocking layer |
US6340789B1 (en) | 1998-03-20 | 2002-01-22 | Cambridge Display Technology Limited | Multilayer photovoltaic or photoconductive devices |
US20020119297A1 (en) * | 1998-08-19 | 2002-08-29 | Forrest Stephen R. | Organic photosensitive optoelectronic devices with transparent electrodes |
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